Aqueous formaldehyde solution stabilized by synergic mixtures of aminotriazine

ABSTRACT

DESCRIBED ARE AQUEOUS FORMALDEHYDE SOLUTIONS CONTAINING OR NOT CONTAINING METHANOL, WHICH REMAIN STABLE FOR LONGER STORAGE TIMES, AT LOWER TEMPERATURE WITH HIGHER CH2O CONCENTRATION. THE SOLUTIONS CONTAIN AS STABILIZING AGENTS SYNERGISTIC MIXES CONSTITUTED BY: (A) MELAMINE OR ITS METHYLOL DERIVATIVES; (B) AT LEAST ONE OF THE GUANAMINE DERIVATIVES OR THEIR METHYLOL DERIVATIVES WHOSE GENERAL FORMULA IS:   2,6-DI(H2N-),4-R-S-TRIAZINE   WHEREIN R MAY BE ALKYL WITH BETWEEN 1 TO 20 CARBON ATOMS, ARYL, A HYDROGENATED ARYL, AN ALKYLARYL, AN ALKYL OR PHENYL SUBSTITUTED ARYL, OR A POLYARYL.

United States Patent 3,658,913 AQUEOUS FORMALDEHYDE SOLUTION STA- BILIZED BY SYNERGIC MIXTURES OF AMINOTRIAZINE Ibrahim Dakli, Busto Arsizio, Varese, Angelo Demicheli, Saronno, Varese, and Giuseppe Gregori, Busto Arsizio, .Varese, Italy, assignors to Montecatini Edison S.p.A.,

Milan, Italy No Drawing. Filed July 15, 1968, Ser. No. 744,624"

Claims priority, application Italy, July 17, 1967,

Int. Cl. C07c 47/04 U.S. Cl. 260-606 1 Claim ABSTRACT OF THE DISCLOSURE Described are aqueous formaldehyde solutions'containing or not containing methanol, which remain stable for longer storage times, at lower temperature with higher (EH 0 concentration. The solutions contain as stabilizin agents synergistic mixes constituted by:

(A) melamine or its'methylol derivatives;

(B) at least one of the guanamine derivatives or their methylol derivatives whose general formula is:

wherein R maybe alkyl with between 1 to 20 carbon atoms, aryl, a hydrogenated aryl, an alkylaryl, an alkyl or phenyl substituted aryl, or a polyaryl.

The present invention has for its object the preparation of stable aqueous formaldehyde solutions with concentrations equal to or greater than 36% by weight, and

optionally containing methanol. The solutions are free' from the precipitation of the paraformaldehyde for longer periods of time and at considerably lower temperatures both with respect to normal non-stabilized formaldehyde solutions as well as to formaldehyde solutions stabilized with means different from those forming the object of this invention and which are usable in all fields of application.

Different processes are known for stabilizing aqueous solutions of formaldehyde in order to delay the abovementioned precipitation phenomenon. It is also known that the greatest part of these processes consists in adding to the solutionsparticular stabilizing agents.

The main known compounds used for this purpose are:

Ser. No. 406,897, now U.S. Pat. No. 3,423,467 of.

Dakli et al);

The compound under (a) has economical and technological drawbacks that often discourage its use. In fact,

3,658,913- Patented Apr. 25, 1972 ice in order to obtain effective stabilization of the formaldehyde solution, considerable quantities must be used (7- 14% by weight on the stabilized formaldehyde solution), which causes considerable economical burdens and a slowing down of the condensation kinetics.

The compounds of (b) and (c), although on one hand they partially eliminate the drawbacks of methanol (slowing down of the condensation kinetics), on the other hand they still must be used in considerable quantities (melamine 2-10% by weight, urea and/or its derivatives 510% by weight on the stabilized solutions), while not allowing the polyvalent use of formaldehyde solutions.

Each of the two types of stabilizers, as a matter of fact, owing to the great quantities in which they are present in the aqueous formaldehyde solutions, restrict the use of the formaldehyde to specific types of condensation' in the sense that the solutions stabilized with melaminewill be used for the preparation of resins based on melamine/ formaldehyde, while the solutions stabilized with urea and/or its derivatives, will be used forthe preparation of resins based on urea/ formaldehyde.

The compounds of point (d) are used in modest quantities (maximum 0.1% by weight on stabilized formalde-" hyde solutions) and the formaldehyde thus obtained may be used for any type of synthesis.

However, the stabilizing effect exerted is rather moderate, particularly at the low storage temperatures.

The compounds of (e) are the most interesting of the known stabilizers inasmuch as, though used with very low concentrations (0.1-0.2% by weight on the stabilized formaldehyde solutions) they impart to the formaldehyde solutions a high stability under low storage temperatures.

Most of the guanamine derivatives, however, are commercially available at rather high prices.

We have surprisingly found that aqueous solutions of formaldehyde, having concentrations equal to or greater than 36%, are stabilized in a much more effective way if, instead of using melamine singly or at least one of the derivatives of guanamine, mixtures of these two compounds are used.

Such mixtures actually show clearly a synergistic effect with regard to the stabilization of the formaldehyde solutions. This is so much the more surprising if one considers the fact thatsuch synergistic action does not exist when mixtures of guanamine derivatives are used to stabilize the formaldehyde solutions.

Thus, this invention represents something new in respect to the prior art inasmuch as:

It allows obtaining formaldehyde solutions which are much more stable for storage (down to 15 C.) than anything known so far.

It allows achieving this effect with much lesser quantities of melamine (of standard industrial manufacture) and of guanamine derivatives than would be necessary, in order to obtain the same effects, when the melamine and the guanamine are used separately I The guanamine derivatives which, according to this invention, act synergistically together with the melamine with regard to the stabilization of the formaldehyde solutions, have the formula:

112N4 3 fi-NHa wherein R may be an alkyl containing between 1 and 20 carbon atoms, an aryl, a hydrogenated aryl, an alkylaryl,

a phenyl or alkyl substituted aryl, or a polyaryl.

,B h th m lamin a wel st a sy indic d. guanamines, may be used in the form of methylol derivatives, of condensates with aldehydes or of organic and. inorganic salts. v

Thelquantities of stabilizer preferably used according to this invention are such that l 0 parts by weight of aqueoussolution of stabilized formaldehyde shall contain from 0.1%..to 1% by weightjof melamine andifrom 0.001% to 0.1% byweight of guanaminederivativesof FormulaI. It is evident, however, .that the melamineguanainine derivative mixtures. are also synergistic for the stabilization of the aqueous formaldehyde solutions in concentrations lower or higher than the limits indicated above.. v r A The stabilization of the formaldehyde solutionsis conducted by reacting .thestabilizing synergistic mixture with the formaldehyde solutions to be. stabilized, within a wide range of temperatures, from 30 C. to 100 C.-, but preferably from 40, to .70' C., for a time comprised between. 30 minutesandv hours. and at a pH value comprised between 2.S and 6.0, but preferably between 3.0 and.5.0. The stabilizingftime is. inversely .proporti onal to the v tern: perature used. f. b

The stability of the formaldehyde solutions grows, as a matter of fact, within certain limits, with the increasing of the'stabilizing timeat a certain temperature and, fora certain stabilizing time, increases within certain limits with the risng of the temperature. The stabilization of the formaldehyde solutions may be carried out in the formaldehyde producing plant, without the need of setting up additional equipment.

The following are a few examples for illustrating this invention without limiting it. Also given are somecomparative examples to show that:

The aqueous formaldehyde solutions stabilized with the individual stabilizers (melamine or guanamine de-. rivatives) show an appreciably smaller stability with respect to the solutions stabilized with the synergistic mixures that are the object of the present invention.

The use of mixtures of guanamine derivatives has no Finally, for clearness sake, it is poined out that in vthe examples the stabilities of the aqueous formaldehyde solutionsare given as the time (in hours or days, depending on the indications) during which they keep free from-the formation of paraformaldehyde and that the. concentra,.

tions of the same solutions and of the stabilizer are expressed in percent by weight. i

EXAMPLES 1- v I 4 N 0.3% by weight of melamine and 0.01% .byweig htof six dilferent guanamine derivatives were added respectively to six samples of a 36% aqueous formaldehydesolution having a pH of 3.5. 3 I; Each sample was then made to react for 43101115 at 50 C. under. stirring and, at reaction completion, was cooled.

down and stored at three'different temperatures C., -10 C. and 0 C.). B. Table lreports the stability values obtained. 1 i.

EXAMPLES 7-11 I A mixture constituted by 0.3% by'weight bf'nielaniin'e and 0.01% by weight of five guanamine derivatives was added to five samples of a 36% formaldehyde solution having a pH of 4.

Each sample was made to react for 6 hours at 40 C. under stirring and, at reaction completion, was cooled down and stored at -15 C. and at 10 C. The stability values obtained are reported in Table 2.

EXAMPLES 12-17 L mixture of'melamine and lauroguana rniiie quantities was added respectively to six sampi tformaldehyde solution having a pH of 3.7. r

v yi

.Each ,smnplewas made to react for 2 hours at 60 C. under stirring and, at reaction completion, was cooled down and then stored at two difierent temperatures. The stability values obtained are reported in Table 3.

i I EXAMPLE18 0.3% b.y .wei ght-of melamine and 0.03% by weight of lauroguanamine were added to a 40% aqueous formaldehyde solution having a pH of 3.2.

The solution thus treated was then made to react for 2 hours at 60" C. under stirring and, atreaction completion, was cooled down and stored at -10 C. and 0 C. The

I stability of the sample stored at l0 C. was 10 days,

while that of the samplestored at0 C. was 30days.

EXAMPLE 19' 0.5% by weight of melamine and 0.05% by weight of lauroguanamine were added toa 45% aqueous formaldehyde solution having a pH of 3.0.

The stability of the sample stored at 0. C.fwas'7 days; the stability of the sample The solution thus treated was then made to reactfor 2 hours at. 60 C. under stirring and, at reajction completion, wascooled down and stored at 0 cganq at +10? C.

EXAMPLE-2 0 1% by vveight of melamine and 0.07% by weight of stored at +10 wa s lip days v lauroguanamine were added to a 50% aqueous formaldewhile the stability of the sample stored at +15 C. was

30 clays.- i

- I ComparativeExamples l-VII I For the comparing of the mainexamplesfrom 1 to 6, 0.3% by weight of melamine or 0.01% by weight of six different guanamine derivatives were added respectively to seven samples of a 36% aqueous formaldehyde solution with a pH of 3.5. l 7

,Each sample was, then made toreact for 4 hours at C. under stirring and, at reactioncompletion, was cooled down and-then stored at three different temperatures (i.e,:

allthe stability values obtained.

' Comparative Examples VIII-XII I For compariri'g the main examplesfromi to .1 1,0;01,

by weight of five different guanamine derivatives were.

added respectively to five samples of a 36% aqueous solu tionof tor naldehyde having apH of 4. .7

Each sample was madeto'react for 6 hours atf 4 10 1C.

under stirring .andQat reactioncompletion, was then cooled. 5C. and at l0 C. Table 5 down and stored at -7 records thestability values obtained. V

Comparative Example X-I II- -XVHI v For comparing the main Examples from 12 to 1'7, varying quantities of melamine and varying quantities 0laur0- guanamine were added to six samples of a 36% aqueous formaldehydesolution having-a pH-of- 3.7.-

Each sample was made to react for 2 hours at 60 C., under stirring, and;at reaction completion; was then stored at -.10.C.-and at 0 C. s .2

Table :6 records all the stability values obtained.

; Comparative EXampIesXDC-XX A .For 'compa'rison with the main Example 18,- 0.3% byweight'of melamine or 0.03% by weight of lauroguanamin'etwere added respectively to'two samples of a aqueous formaldehyde solution having a pH of 3.2.

The solution thus treated were then made to react for cooled down and then's to'red at 10 C., and at0 C.

. 6 -T 7 -rea rdse l. t e. ete ilitmeleetaltered: TABLE 3 comparative EXmPIeSXXLXXH Examples from 12 to l7St ability of 36% formaldehyde solutions treated with mixes of lauroguanamine and For comparison with the main Example l9-, to two-sar'n- 5 melamine in varying quantitiesples of a 45% aqueous formaldehyde solution having a pH of 3.0, werevadded 0.5% by weight of melamine or Y W n Mixture oistabmzers t ife 'iiiige r itifil oi 0.05% by weight of lauroguanamine, p Quantity. 'The solutions thus treated weremade' to reactfor 2 Type percent o hours at 60 C. under stirring and, at reaction completion, 10 12 hai iroi uanemineuu 0 4 15 were cooled down and then stored at 0 C. and at C; g 0, 6 13 30 Table 8 record s all the stability values obtained.- e .0.2 N 14 a111r0giuanamlne. 0.80; 15 30 e am he Comparative Examples XXIII-XXIV: 15 {Laur0guanamine... 0.001 5 I Melamine 8 For comparison with the main Example 20,31'% by min '02} weight, of melamine or 0.07%.. by'weight oflauroguane {;fz f fi z 8 3} 10 amine were added respectively tothe two samples of a n 50% aqueous formaldehyde solution having a pH of 3.0. 7 The solutions thus treatedwerethen made to'react for 20 v 1 TABLE 4 I one hour at 70 C. un e Stirring and, atTTeacfiOn Comparative examples from I to VII-aStability of 36% pletwn, were cooled down and then d t 0 aqueous formaldehyde solutions treated with either melandat +15 C. r amine alone at 0.3% by weight or with only guanamine Table 9 records allthe stability value'sobtained. derivatives at0.0l% by weight. r I i Q v I p Stab'lizer Stability at the temperature of- ,Cor'nparative v v Quantity,

example Type V I percent 715 C. 10 C 0 C.

0.3 10 hours..." lday.-- 8days. e e 8: .,.,l' g r:-- .-.-.g

. a 0. 2 dags. 0. 6 days. 0. 15 days.

* 0. 1 day.

Comparative Examples X XV-XXVII To three samples of a 36% aqueous solution of forrri- Comparative examples VIII to XII-Stability of" 36% aldehyde havinga pH of 3.5, were added mixes of g'uanformaldehyde' solutions treated with 0.01% by weight of:

amine derivatives in quantities of the same order as those some of the guanamine derivatives. according to thisinventi'on. Each sample was made-to react for 4 hours at 50 C: 40 under stirring and, on completion of the reaction, was gig g i Type stabilizer W then cooled down and stored at two difierent temperatures Stability at a temperature of- ..d. e a-p BUY enzoguana 119...-.. 0 0111'shyde solutions at 36%, treated under the same conditions XII Bemmphthoguanamine 10 houm with the single guanamine derivatives not in admixture with each other. TABLE 6 ABL T Comparative examples from XIII to XVIHStability P P from 6Stab1hty P 36% formaldehyde of 36% formaldehyde solutions treated with melamine solutions treated with 0.3% by weight of melamine and only or with lauroguanamine only with 0.01 by Weight of gnanamine.

Stability in days at Stabilizer Stability at a temperature oi the temperature of Comparative Quantity, 0 0 Example Mixture of stabilizers used 15 C. 10 0. 0 C. example Type Percent 0 Melamine 0.1 5 hours... 3 days. 1 Proploguanamine-melarnine 2 5 2. Caproguanamine-melamine. 3 8 20 d 0 l h l l 3-. Caprylguanamine-melamine-- 5 12 30 0-002 1 d ours- 4-- gaprlnoguanamine-nlielamine- 1; 33 33 0'00? 25 2% 5-. auro anamine-me amine... 6 Benzog uanamine-melamineu. 5 10 (1005 1 day 7 days- TABLE 2 TABLE 7 Exflmples from y of 36% f l y Comparative examples from XIX and XX-Smbility solutlons treated wi h r of 0.3% f m lamme and or 40% formaldehyde solutions treated either with mel- 0-01% of gllaflamme derlvatlvesamine alone at 0.3% by weight or with lauroguanamine stability in days at 5 alone at 0.03% by weight. the temperature of- Example Mixture of stabilizers used l5 C. -10 C. C a stab -mzerQ m teilg i r o i ompara ve nan 7 igglfig 3 6 example Type percegt -10c. 0 0. 8 ggggigg 3 8 XIX. Melamine 0.03 10 hours--- 1 day. 9 Meta butylb'euzoguanamine 8 20 XX-. Laur0guanamine.. 0.03 1 day 9 days.

melamine. 10 Meta-phenylbenzoguanamine- 10 30 TABLE 8 melamine. z g rg g e 12 Comparative examples from XXI to XXII-Stability of 45% formaldehyde solutions treated with melamine r 8 only at 0.5% by weight or with lauroguanamine alone at Stagflizr Stability at a 0.05% by weight. I I temperature of- Comparative Quantity,

example Type V a I pereent 10C. C.

.,.,. 7. Lauroguanamina 0.005 1 day.... 8 days.

XXV Benzoguanamine stability {Lauroguanamine..-- 0.005 -do 7 days.

7 Stabilizer temp ratur Benzoguanamine 0. 01 hours... 1 day. comparative Quantity mi {a u na-a at? em p p p C- f f' fdfif l jl 03g; nfidhoursu. a d s.

- auroguana 8.--- V ay ays; x1 Mmmin 0.51 1h 6h ogmma XII L ms nammen 0.05 16 123115--- 662;: m f igfi i i .E TII 813i do 6 days.

Weclaim: I 1. An aqueous formaldehyde solution of at least 36% TABLE 9 concentration, containing by weight of aqueous solution of stabilized formaldehyde as a stabilizing agent a mix of Comparative examples from XXIII to XX-IVAtabIhtY (A) 0.1 to 1.0% melamine or its methylol derivatives; of 50% formaldehyde solutions treated with melamine d 310116 at 1% y Weight with lallfogllanamine alone at (H) 0.001 to 0.1% of atleast one guanamine derivative 037% y tor its-methy1o1 derivatives selected from the group I consisting of propioguanamine, caproguanamine,

caprylguanamine, caprinoguanamine, lauroguanr amine, benzoguanamine, tetrahydrobenzoguanamine, so Stability MB 7.1m. phenyl acetohenzoguanamine, meta-butyl benzo- Y i Stabilizer i r of guanamine, meta-phenylbenzo-guanamine and betatit 3325?? V6 Type iceit 0 0. +10 (2. nsphihoguanamme- Lxfurogmfinamina- 0.0% 30m.-- idggs f References Clted UNITED STATES PATENTS 3,423,467 1/1969 Dakli et a1. 26O606 r 7 2,237,092 4/1941 Swain 260606 M f TABLE 10 I l, V j r FOREIGN PATENTS Y a Comparative examples from XXV to XXVIH Zompari- 1,029,039 5/1966 Great ai 260-4506 sonbetween the stability of 36% aqueous formaldehyde 1,205,073 11/1965 G solutions treated with mixtures of guanamin'e' and that of 1 y I 36%1formaldehyde solutions treated underthe'sameeon BERNARD HELFIN Pmnary Exammel' ditions but with the single guanamine in the quantities R, HJ Assistant Examiner foreseen by our invention. 40 v 

